CN114196438B - Hydrogenation process and hydrogenation system for treating high-nitrogen raw material - Google Patents
Hydrogenation process and hydrogenation system for treating high-nitrogen raw material Download PDFInfo
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- CN114196438B CN114196438B CN202010981455.1A CN202010981455A CN114196438B CN 114196438 B CN114196438 B CN 114196438B CN 202010981455 A CN202010981455 A CN 202010981455A CN 114196438 B CN114196438 B CN 114196438B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 160
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 83
- 239000002994 raw material Substances 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 204
- 238000006243 chemical reaction Methods 0.000 claims abstract description 163
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 239000003350 kerosene Substances 0.000 claims description 17
- 239000002283 diesel fuel Substances 0.000 claims description 16
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 description 20
- 238000007670 refining Methods 0.000 description 14
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000005336 cracking Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a hydrogenation process and a hydrogenation system for treating a high-nitrogen raw material, wherein the hydrogenation process comprises the steps of firstly separating the high-nitrogen raw material to obtain a low-nitrogen fraction and a high-nitrogen fraction, respectively feeding the low-nitrogen fraction and the high-nitrogen fraction into a hydrofining reaction zone through different feed inlets, carrying out hydrogenation reaction in the presence of hydrogen and a catalyst, feeding a reaction effluent into a hydrocracking reaction zone for further reaction, and separating to obtain a target product. The hydrogenation process can flexibly process poor-quality high-nitrogen raw materials under mild operation conditions, simultaneously prolongs the operation period of the whole hydrogenation system, and solves the problems of shortened service life of the catalyst and poor economic benefit of the device caused by the mode of reducing feeding amount, increasing reaction temperature and the like in the prior art.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and relates to a method and a system for hydrotreating a high-nitrogen raw material, in particular to a hydrocracking method and a hydrocracking system for flexibly processing a high-nitrogen inferior raw material.
Background
With the continuous aggravation of crude oil heaviness and the emphasis on the regulator function of hydrocracking in the refining integration, the hydrocracking raw material source presents a trend of increasing heaviness, the nitrogen-containing compounds in the hydrocracking raw oil are greatly improved, the improvement of the nitrogen-containing compounds can firstly inhibit the activity of a hydrocracking catalyst, so that the catalyst is inactivated to influence the operation of a device, and secondly, the nitrogen-containing compounds are difficult to remove, so that the product quality is also greatly influenced. When the nitrogen content in the raw oil fluctuates greatly or abnormally increases, the production operation difficulty of the device can be increased sharply, and the airspeed is required to be reduced or the reaction temperature of the section is required to be increased to realize the nitrogen content fluctuation. Meanwhile, the reaction temperature of the refining section is increased, so that the outlet temperature of the refining section is not matched with the inlet temperature of the cracking section, a large amount of cold hydrogen is needed, and huge economic loss is caused.
CN1940030A discloses a hydrocracking method for producing diesel oil in high yield from high-nitrogen raw material, wherein high-nitrogen raw material oil is treated by a first hydrofining reactor, generated oil enters a thermal flash tank for gas-liquid separation and then enters a second hydrofining reactor, and the dosage of a hydrofining catalyst can be effectively reduced by processing high-nitrogen inferior raw material under mild process conditions. The patent processes high-nitrogen raw materials by adding a refining reactor, greatly increases equipment investment and catalyst purchase cost, and has the defects of poor fixed flexibility of the process flow, insufficient utilization of the catalyst in the refining section, poor economic benefit and the like.
CN103102966A discloses a hydrocracking method for treating high-nitrogen raw material, and adopts two-stage technological process, and the denitrogenation rate of the first-stage reaction zone is controlled to be 60-95%, and the heavy tail oil obtained by gas-liquid separation of first-stage reaction effluent can be fed into second reaction zone to further denitrogenate. The method actually treats the high-nitrogen raw material by additionally arranging a refining reactor, and simultaneously increases a separation system, so that the method has the defects of high equipment investment, high catalyst purchasing cost and the like.
CN103773481A discloses a combined hydrocracking method for treating inferior raw material, which adopts a counter-current process to pretreat high-nitrogen raw material, and adopts a parallel-current process to treat conventional raw material. The high-nitrogen raw material which can be treated by the method has the requirements on nitrogen content, and meanwhile, the method has the disadvantages of complex process, large equipment investment and poor economical efficiency.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation process and a hydrogenation system for treating a high-nitrogen raw material. The process can flexibly process the inferior high-nitrogen raw material under mild operation conditions, simultaneously prolongs the operation period of the whole hydrogenation system, and solves the problems of shortened service life of the catalyst and poor economic benefit of the device caused by the mode of reducing the feeding amount, increasing the reaction temperature and the like in the prior art.
The invention firstly provides a hydrogenation process for treating a high-nitrogen raw material, which comprises the following steps: separating the high-nitrogen raw material to obtain a low-nitrogen fraction and a high-nitrogen fraction; the high-nitrogen fraction enters a hydrofining reaction zone through a feed inlet at the top of the hydrofining reaction zone, the low-nitrogen fraction enters the hydrofining reaction zone through a feed inlet at the middle lower part of the hydrofining reaction zone, hydrogenation reaction is carried out in the presence of hydrogen and a catalyst, a reaction effluent enters a hydrocracking reaction zone for further reaction and is separated to obtain a target product, and the target product can comprise but is not limited to naphtha, aviation kerosene, diesel oil, tail oil and the like according to needs; it is further preferred that the aviation kerosene and/or diesel oil is recycled to the hydrotreating reaction zone, and it is further preferred that the aviation kerosene and/or diesel oil enters the hydrotreating reaction zone through the middle-lower feed port to be mixed with the low nitrogen fraction.
In the above hydrogenation process for treating high-nitrogen raw material, the high-nitrogen raw material is a heavy hydrocarbon-containing material with nitrogen content of more than 1800 μ g/g, preferably with nitrogen content of 2000-5000 μ g/g and sulfur content without special limitation, and the initial boiling point of the high-nitrogen raw material is generally 270-330 ℃ and the final boiling point is generally 460-560 ℃. The high-nitrogen raw material can be one or more of deep-drawing vacuum wax oil, coking gas oil, deasphalted oil, coal tar and coal liquefaction oil.
In the hydrogenation process for treating the high-nitrogen raw material, the division point temperature of the low-nitrogen fraction and the high-nitrogen fraction is 300-400 ℃, and preferably 320-360 ℃.
In the above hydrogenation process for treating a high-nitrogen feedstock, the hydrofining reaction zone and the hydrocracking reaction zone may be disposed in 1 reactor, or may be disposed in one or more independent reactors. The hydrofining reaction zone is provided with more than 3 hydrofining catalyst beds, preferably 3-5 hydrofining catalyst beds, and further preferably 3-4 hydrofining catalyst beds. The hydrocracking reaction zone is provided with more than 1 hydrocracking catalyst bed layer.
In the above hydrogenation process for treating a high-nitrogen raw material, the feed inlet at the lower middle part of the hydrofining reaction zone is located between any two hydrofining catalyst beds in the hydrofining reaction zone, and is preferably arranged between the two catalyst beds at the lowest part in the flowing direction of the liquid-phase material, and specifically when 3 hydrofining catalyst beds are arranged, the feed inlet can be arranged between the first hydrofining catalyst bed and the second hydrofining catalyst bed and/or between the second hydrofining catalyst bed and the third hydrofining catalyst bed; preferably arranged between the second hydrofining catalyst bed and the third hydrofining catalyst bed; by analogy, the specific arrangement position of the feed inlet can be selected according to the arrangement quantity of the hydrorefining catalyst bed layers and the filling type of the catalyst.
In the hydrogenation process for treating the high-nitrogen raw material, the operation conditions of the hydrofining reaction zone are as follows: the hydrogen partial pressure is 5 to 18MPa, preferably 8 to 16MPa; the volume ratio of the hydrogen to the oil is 500 to 5000, preferably 700 to 1500; the volume space velocity is 0.5 to 3 hours -1 Preferably 0.7 to 2 hours -1 (ii) a The reaction temperature is 260 to 420 ℃, preferably 300 to 400 ℃.
In the hydrogenation process for treating the high-nitrogen raw material, the operating condition of the hydrocracking reaction zone is that the hydrogen partial pressure is 6-18 MPa, preferably 7-17 MPa; the volume ratio of the hydrogen to the oil is 500 to 5000, preferably 700 to 1500; the volume space velocity is 0.2 to 5 hours -1 "YouyouIs selected to be 0.6 to 2 hours -1 (ii) a The reaction temperature is 270 to 460 ℃, preferably 300 to 400 ℃.
In the above hydrogenation process for treating a high-nitrogen feedstock, the hydrofining catalyst in the hydrofining reaction zone generally comprises a carrier and an active metal component, wherein the carrier is one or more of inorganic refractory metal oxides such as alumina and silica, preferably alumina; the active metal component is one or more of VIB and/or VIII group metals; for example, the material can be one or more of W, mo, ni and Co, and Ni and Mo are preferred. Generally, the group VIB metal component is present in an amount of from 10 wt.% to 30.0 wt.%, preferably from 11.5 wt.% to 25.5 wt.%, calculated as metal oxide; the content of the VIII group metal component is 0.1wt% to 8.0wt%, preferably 2wt% to 6wt%.
In the hydrogenation process for treating the high-nitrogen raw material, along the flowing direction of the liquid-phase material, the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer above the feeding hole at the middle lower part is gradually reduced, and the difference of the pore volume of the hydrofining catalyst in the adjacent hydrofining catalyst bed layers is 0.01-0.40 mL/g, preferably 0.03-0.22 mL/g. The pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer below the middle-lower feed port is not less than that of the hydrofining catalyst in the hydrofining catalyst bed layer above the middle-lower feed port, and the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer at the top of the hydrofining reaction zone is generally 0.30-0.50 mL/g, and preferably 0.34-0.40 mL/g.
In the hydrogenation process for treating the high-nitrogen raw material, the content of the active metal component of the hydrofining catalyst in the hydrofining catalyst bed layer above the feed inlet at the middle lower part is gradually reduced along the flowing direction of the liquid-phase material, and the content of the active metal component of the hydrofining catalyst in two adjacent hydrofining catalyst bed layers is different by 0.1-3.0 wt% and preferably 0.5-2.0 wt% in terms of metal oxide; wherein the content of the group VIB metal components differs by 0.1wt% -3.0 wt%, preferably by 0.5wt% -1.5 wt%; the amounts of the group VIII metal components differ by 0.1wt% to 2.0wt%, preferably by 0.2wt% to 1.0wt%. The content of the active metal component of the hydrofining catalyst in the hydrofining catalyst bed layer below the feed inlet at the middle lower part is not less than the content of the active metal component of the hydrofining catalyst in the hydrofining catalyst bed layer at the top of the hydrofining reaction zone, and the content of the active metal component is preferably 0.1-5.0 wt% and more preferably 0.5-2.0 wt% higher than the content of the active metal component of the hydrofining catalyst in the hydrofining catalyst bed layer at the top, calculated by metal oxide.
In the above hydrogenation process for treating a high-nitrogen raw material, it is further preferable that the hydrofining catalyst includes an auxiliary agent fluorine, and along the flow direction of the liquid-phase material, the loading amounts of fluorine in the hydrofining catalyst are sequentially increased, and the loading amounts of fluorine in the hydrofining catalyst beds of two adjacent layers of hydrofining catalyst beds are sequentially increased by 0.2 to 2.0wt%, preferably 0.3 to 0.5wt%. The loading amount of fluorine in the hydrofining catalyst is generally 0.1 to 7.0wt%, and preferably 0.1 to 3.5wt%.
In the above hydrogenation process for treating a high-nitrogen feedstock, the catalyst used in the hydrocracking reaction includes a cracking component and a hydrogenation component. The cracking component typically comprises amorphous silica alumina and molecular sieve. The hydrogenation component is one or more of non-noble metal elements in VI group, VII group or VIII group, preferably two or more metals of Co, mo, ni and W are used as active components. Based on the weight of the catalyst, the content of the hydrogenation component is 10-40 percent calculated by oxide. The catalyst can be any commercial hydrocracking catalyst, different types of hydrocracking catalysts are selected according to different target products, light oil type hydrocracking catalysts can be selected for naphtha, medium oil type hydrocracking catalysts can be selected for medium distillate, and flexible hydrocracking catalysts can be selected for naphtha and medium distillate which need to be flexibly produced. For example, commercial hydrocracking catalysts such as FC-52, FC-70, FC-76 and FC-32 developed by the Fushun petrochemical research institute (FRIPP) may be prepared as required according to common knowledge in the art.
In another aspect, the present invention provides a hydrogenation system for treating a high nitrogen feedstock, the hydrogenation system comprising:
a fractionating tower: the method comprises the steps of receiving a high-nitrogen raw material, and separating to obtain a low-nitrogen fraction and a high-nitrogen fraction;
a hydrofining reaction zone: the hydrofining reaction zone comprises a top feeding hole, a middle lower feeding hole and a bottom discharging hole; the high-nitrogen fraction enters a hydrofining reaction zone through a top feed inlet, the low-nitrogen fraction enters a hydrofining reaction zone through a middle-lower feed inlet, and reacts in the presence of hydrogen and a hydrofining catalyst to obtain a hydrofining reaction effluent after reaction;
a hydrocracking reaction zone: leading out the hydrofining reaction effluent from a discharge port at the bottom of the hydrofining reaction zone, introducing the hydrofining reaction effluent into a hydrocracking reaction zone, and reacting in the presence of hydrogen and a hydrocracking catalyst;
the gas-liquid separation unit is used for receiving the reaction effluent from the hydrocracking reaction zone and separating the reaction effluent to obtain a gas-phase material and a liquid-phase material;
and the fractionating unit is used for receiving the liquid-phase material from the gas-liquid separation unit and separating the liquid-phase material to obtain gas, naphtha, aviation kerosene, diesel oil and tail oil.
In the above hydrogenation system for processing a high-nitrogen feedstock, the hydrofining reaction zone and the hydrocracking reaction zone may be disposed in 1 reactor, or may be disposed in one or more independent reactors. The hydrofining reaction zone is provided with more than 3 hydrofining catalyst beds, preferably 3-5 hydrofining catalyst beds, and further preferably 3-4 hydrofining catalyst beds. The hydrocracking reaction zone is provided with more than 1 hydrocracking catalyst bed layer.
In the above hydrogenation system for processing high-nitrogen feedstock, the aviation kerosene and/or diesel oil may be recycled back to the hydrorefining reaction zone through a pipeline, and further preferably enter the hydrorefining reaction zone through a middle-lower feed inlet to be mixed with the low-nitrogen fraction.
In the above hydrogenation system for treating a high-nitrogen feedstock, the feed inlet at the lower middle portion of the hydrofining reaction zone is located between any two hydrofining catalyst beds in the hydrofining reaction zone, and is preferably arranged between the two catalyst beds at the lowest portion in the flowing direction of the liquid-phase material, and specifically when 3 hydrofining catalyst beds are arranged, the feed inlet can be arranged between the first hydrofining catalyst bed and the second hydrofining catalyst bed and/or between the second hydrofining catalyst bed and the third hydrofining catalyst bed; preferably arranged between the second hydrofining catalyst bed and the third hydrofining catalyst bed; by analogy, the specific arrangement position of the feed inlet can be selected according to the arrangement quantity of the hydrorefining catalyst bed layers and the filling type of the catalyst.
In the above hydrogenation system for processing high-nitrogen raw materials, the arrangement of the fractionating tower, the gas-liquid separation unit and the fractionating unit can adopt the existing arrangement mode in the field. The gas-liquid separation unit comprises a hot high-pressure separator, a hot low-pressure separator, a cold high-pressure separator and a cold low-pressure separator, and the fractionating unit comprises more than one fractionating tower, and the fractionating tower can adopt any one of the devices which can realize oil product separation in the prior art, such as a packed tower and a plate tower.
Compared with the prior art, the hydrogenation process and the hydrogenation system for treating the high-nitrogen raw material have the following advantages:
1. in the hydrogenation process for treating the high-nitrogen raw material, the high-nitrogen raw material is firstly separated and reasonably graded in a hydrofining reaction zone, the pore volume of a catalyst in the hydrofining reaction zone is firstly reduced and then increased from top to bottom, the hydrogenation activity is in a reduction trend, the hydrogenolysis capacity is in an increase trend, high-nitrogen fraction rich in condensed ring nitrogen-containing compounds (such as carbazole and the like) is firstly subjected to heterocyclic hydrogenation saturation reaction on a catalyst bed layer with strong hydrogenation activity at the upper part, and the poor-quality high-nitrogen raw material can be treated under mild operation conditions while the operation period of the whole hydrogenation system is prolonged. The problems that the service life of the catalyst is shortened and the economic benefit of the device is poor due to the fact that modes such as reducing feeding amount and improving reaction temperature are relied on in the prior art are solved.
2. In the hydrogenation process for treating the high-nitrogen raw material, the high-nitrogen fraction flows through all catalyst beds in the whole hydrogenation refining reaction zone, the volume space velocity of the hydrogenation refining catalyst bed at the upper part of the hydrogenation refining reaction zone is obviously reduced due to the cutting-out of the low-nitrogen fraction, the removal of nitrogen impurities in the high-nitrogen fraction is realized through the catalyst with strong hydrogenation activity at the upper part, and meanwhile, the impurities in the raw material enter the hydrogenation refining reaction zone from the feed inlet at the middle lower part of the reactor, so that the impurities are not concentrated and accumulated on the catalyst bed at the uppermost layer, but are uniformly distributed in the whole reaction zone, and the operation period of the hydrogenation refining reaction zone is prolonged.
3. In the hydrogenation process for treating the high-nitrogen raw material, the high-nitrogen raw material is firstly separated and reasonably graded in the hydrofining reaction zone, so that the temperature rise of the uppermost catalyst bed layer of the hydrofining reaction zone and the outlet temperature of the reaction zone are obviously reduced, the temperature rise of each bed layer is uniform, the economic benefit brought by the consumption of cold hydrogen is reduced, and the operation difficulty is also obviously reduced. The problems that in the prior art, the temperature rise of the whole reaction zone is not uniformly distributed (the temperature rise of a hydrofining reaction zone is mainly concentrated on the uppermost catalyst bed layer, and the temperature rise of the lower part of the reaction zone is obviously lower than that of the upper part of the reaction zone), a large amount of cold hydrogen needs to be injected between the catalyst bed layers to increase the operation cost, and meanwhile, the outlet temperature of the hydrofining reaction zone is higher and the inlet temperature of a cracking reaction zone is not matched are solved.
4. In the hydrogenation process for treating the high-nitrogen raw material, the middle distillate (diesel oil and aviation kerosene) is circulated to the hydrofining reaction zone through the feeding port at the middle lower part, so that on one hand, the chemical raw materials (naphtha and tail oil) can be produced to the maximum extent, and the product quality can be improved. Compared with the prior art that the middle fraction is recycled to the hydrocracking reaction zone, the route is more reasonable, and the economical efficiency is greatly improved.
Drawings
FIG. 1 is a schematic diagram of a hydrogenation process and a hydrogenation system for treating a high nitrogen feedstock in accordance with the present invention.
Detailed Description
The operation and effect of the method of the present invention will be further described with reference to the drawings and examples, but the following examples are not intended to limit the present invention.
As shown in fig. 1, the hydrogenation process for treating a high-nitrogen feedstock according to the present invention comprises the following steps: the high-nitrogen raw material 1 firstly enters a fractionating tower 2 and is cut and separated to obtain a low-nitrogen fraction 3 and a high-nitrogen fraction 4, wherein the high-nitrogen fraction 4 and new hydrogen 17 enter a hydrofining reaction zone 5 through a feed port at the top of the hydrofining reaction zone, the low-nitrogen fraction 3 and the new hydrogen 17 enter the hydrofining reaction zone 5 through a feed port at the middle lower part of the hydrofining reaction zone, hydrogenation reaction is carried out in the presence of hydrogen and a catalyst, a reaction effluent hydrofining oil 6 of the hydrofining reaction zone enters a hydrocracking reaction zone 7 for further reaction such as ring opening and chain scission, a hydrocracking reaction effluent 8 enters a gas-liquid separation unit 9 and is separated to obtain a gas-phase component 10 and a liquid-phase component 11, wherein the gas-phase component 10 is treated by a compressor 18 and then used as recycle hydrogen and can be recycled to the hydrofining reaction zone and the hydrocracking reaction zone, the liquid-phase component 11 further enters a fractionating tower 12, and naphtha 13, aviation kerosene 14, diesel 15 and tail oil 16 are obtained after fractionation; the aviation kerosene 14 and/or diesel oil 15 can be recycled to the hydrofining reaction zone 5 through the middle and lower feed inlet of the hydrofining reaction zone to be mixed with the low-nitrogen fraction 3 for treatment.
Example 1
The high nitrogen feed properties are shown in table 1, using the process scheme shown in figure 1, where neither diesel nor aviation kerosene is recycled. The fractionating tower cuts the high-nitrogen raw material into a low-nitrogen fraction (276-360 ℃) and a high-nitrogen fraction (360-549 ℃). The hydrofining reaction zone comprises three catalyst bed layers, and hydrofining catalyst carriers in the three catalyst bed layers are all alumina. Wherein the first bed layer is filled with a hydrofining catalyst A-1, the pore volume of the hydrofining catalyst A-1 is 0.34mL/g, and the loading amounts of Ni and Mo calculated by metal oxides are 3.0wt% and 23.0wt% respectively. The second bed layer is filled with a hydrofining catalyst B-1, the pore volume of the hydrofining catalyst B-1 is 0.32mL/g, and the loading amounts of Ni and Mo are respectively 2.5wt% and 22.0wt% in terms of metal oxide; the F content was 0.6wt%; the third bed layer is filled with a hydrofining catalyst C-1, the pore volume of the hydrofining catalyst C-1 is 0.34mL/g, the loading amounts of Co and Mo are respectively 3.5wt% and 24.0wt% and the content of F is 2.6wt% in terms of metal oxide. The total loading of the hydrofining catalyst is 100mL, and the hydrofining catalyst A-1: hydrofining catalyst B-1: the volume loading ratio of the hydrorefining catalyst C-1 was 20. The hydrocracking reaction area is filled with 100mL of FC-76 catalyst developed by China petrochemical smoothing petrochemical processing institute (FRIPP), and the nitrogen content of the refined oil is controlled to be not more than 10 mug -1 The cracking depth (> 360 ℃) is 70%, the process conditions are shown in Table 2, and the experimental results are shown in Table 3.
Example 2
The properties of the high-nitrogen raw material are shown in table 1, and the process flow shown in fig. 1 is adopted, wherein the middle distillate aviation kerosene 14 and diesel oil 15 are all circulated back to the hydrofining reaction zone through a feeding port at the middle lower part of the hydrofining reaction zone so as to achieve the production purpose of producing chemical raw materials (naphtha and tail oil) to the maximum. The fractionating tower cuts the high-nitrogen raw material into a low-nitrogen fraction (276-320 ℃) and a high-nitrogen fraction (320-549 ℃). The hydrofining reaction zone comprises three catalyst bed layers, and hydrofining catalyst carriers in the three catalyst bed layers are all alumina. Wherein the first bed layer is filled with a hydrofining catalyst A-2, the pore volume of the hydrofining catalyst A-2 is 0.40mL/g, and the loading amounts of Ni and Mo calculated by metal oxides are respectively 6.0wt% and 25.5wt%; the F content was 0.5wt%; the second bed layer is filled with a hydrofining catalyst B-2, the pore volume of the hydrofining catalyst B-2 is 0.38mL/g, and the loading amounts of Ni and Mo calculated by metal oxides are 5.8wt% and 24.0wt% respectively; the F content was 1.0wt%; the third bed layer is filled with a hydrofining catalyst C-2, the pore volume of the hydrofining catalyst C-2 is 0.38mL/g, and the loading amounts of Ni and Mo are respectively 6.3wt% and 26.1wt% calculated by metal oxides; the F content was 1.3wt%. The total loading of the hydrofining catalyst is 100mL, and the total loading of the hydrofining catalyst A-2: hydrorefining catalyst B-2: the volume loading ratio of the hydrofining catalyst C-2 is 40 -1 The cracking depth (> 360 ℃) is 70%, the process conditions are shown in Table 2, and the experimental results are shown in Table 3.
Example 3
The high nitrogen feed properties are shown in table 1, using the process scheme shown in figure 1, wherein only diesel is recycled to the hydrofinishing reaction zone. The fractionating tower cuts the high-nitrogen raw material into two parts of low-nitrogen fraction (276-340 ℃) and high-nitrogen fraction (340-549 ℃), the hydrofining reaction zone comprises three catalyst beds, and hydrofining catalyst carriers in the three beds are all alumina. Wherein the first bed layer is filled with a hydrofining catalyst A-3, the pore volume of the hydrofining catalyst A-3 is 0.39mL/g, the loading amounts of Ni and Mo calculated by metal oxides are respectively 4.5wt% and 24.0wt%, and the content of F is 0.3wt%; (ii) a The second bed layer is filled with a hydrofining catalyst B-3, having a pore volume of 0.38mL/g, ni and Mo loadings of 3.8wt% and 23.2wt%, respectively, in terms of metal oxide, and an F content of 0.6wt%; the third bed layer is filled with hydrofining catalyst C-3, the pore volume is 0.39mL/g, the loading amounts of Ni and Mo calculated by metal oxide are 5.0wt% and 24.3wt%, respectively, and the F content is 1.0wt%. The total loading of the hydrofining catalyst is 100mL, and the hydrofining catalyst A-3: hydrofining catalyst B-3: the volume loading ratio of the hydrorefining catalyst C-3 was 30. The hydrocracking reaction area is filled with 100mL of FC-32 catalyst developed by China petrochemical smoothing petrochemical research institute, and the nitrogen content of the refined oil is controlled to be not more than 10 microgram -1 The cracking depth (> 360 ℃) was 70%, the process conditions are shown in Table 2, and the experimental results are shown in Table 3.
Comparative example 1
The properties of the high-nitrogen raw material are shown in table 1, the conventional single-stage series process flow is adopted, the high-nitrogen raw material is not subjected to fractionation treatment, and all the raw materials sequentially enter a hydrofining reaction zone and a hydrocracking reaction zone which are arranged in series, wherein the catalyst filling of the hydrofining reaction zone and the hydrocracking reaction zone is consistent with that of example 1. The process conditions are shown in Table 2, and the experimental results are shown in Table 3.
Comparative example 2
The properties of the high-nitrogen raw material are shown in table 1, the conventional single-stage series process flow is adopted, the high-nitrogen raw material is not subjected to fractionation treatment, and all the raw materials sequentially enter a hydrofining reaction area and a hydrocracking reaction area which are arranged in series, wherein the hydrofining reaction area is only filled with 100mL of FF-36 hydrofining catalyst developed by China petrochemical industry research institute, the pore volume of the hydrofining catalyst is 0.36mL/g, the loading amounts of Ni and Mo calculated by metal oxides are respectively 2.9wt% and 23.6wt%, and the hydrocracking reaction area is filled with 100mL of FC-76 catalyst developed by China petrochemical industry research institute. The process conditions are shown in Table 2, and the experimental results are shown in Table 3.
TABLE 1 high Nitrogen feedstock Properties
TABLE 2 reaction conditions
TABLE 3 product distribution and product Properties
Data analysis of the above examples 1-3 and comparative examples 1-2 shows that in the hydrocracking process flow provided by the invention, the heavy raw material is divided into light and heavy parts, the light and heavy parts enter the refining reactor from different positions of the refining reactor and are combined with reasonable grading of the refining catalyst, the reaction activity of the hydrofining catalyst can be fully exerted when the hydrocracking raw material with high nitrogen content is treated, and the nitrogen content of the refined oil is controlled to be lower than 10 microgram g -1 Meanwhile, the temperature of a hydrofining reaction zone is obviously lower than that of the prior art, the product structure can be flexibly adjusted and optimized, the yield of heavy naphtha and the product properties of aviation kerosene, diesel oil and tail oil are improved to a certain degree, and remarkable economic benefits are brought to refineries.
Claims (35)
1. A hydrogenation process for treating a high nitrogen feedstock, said hydrogenation process comprising: separating the high-nitrogen raw material to obtain a low-nitrogen fraction and a high-nitrogen fraction; wherein, the high nitrogen fraction enters a hydrofining reaction zone through a feed inlet at the top of the hydrofining reaction zone, the low nitrogen fraction enters the hydrofining reaction zone through a feed inlet at the middle lower part of the hydrofining reaction zone, hydrogenation reaction is carried out in the presence of hydrogen and a catalyst, and a reaction effluent enters a hydrocracking reaction zone for further reaction and is separated to obtain a target product;
the high-nitrogen raw material is a heavy hydrocarbon-containing material with the nitrogen content of more than 1800 mu g/g, the initial boiling point of the high-nitrogen raw material is 270-330 ℃, and the final boiling point is 460-560 ℃; the temperature of the division point of the low-nitrogen fraction and the high-nitrogen fraction is 300-400 ℃;
along the flowing direction of the liquid phase material, the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer above the feed inlet at the middle lower part is gradually reduced, and the pore volume difference of the hydrofining catalyst in the adjacent hydrofining catalyst bed layers is 0.01-0.40 mL/g;
along the flowing direction of the liquid phase material, the content of active metal components of the hydrofining catalyst in the hydrofining catalyst bed layer above the feed inlet at the middle lower part is gradually reduced, and the content of the active metal components of the hydrofining catalyst in the hydrofining catalyst bed layers at two adjacent layers is different by 0.1-3.0 wt% calculated by metal oxides, wherein the content of the VIB group metal components is different by 0.1-3.0 wt%, and the content of the VIII group metal components is different by 0.1-2.0 wt%.
2. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the target products include but are not limited to naphtha, aviation kerosene, diesel oil, and tail oil according to requirements.
3. A hydrogenation process for treating a high nitrogen feed as recited in claim 2, wherein: recycling the aviation kerosene and/or diesel oil to the hydrofining reaction area.
4. A hydrogenation process for treating a high nitrogen feed as recited in claim 2, wherein: and (3) enabling the aviation kerosene and/or diesel oil to enter a hydrofining reaction area through a middle-lower part feed inlet to be mixed with the low-nitrogen fraction.
5. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the nitrogen content of the high-nitrogen raw material is 2000-5000 mug/g.
6. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the high-nitrogen raw material is one or more of deep-drawing vacuum wax oil, coking gas oil, deasphalted oil, coal tar and coal liquefaction oil.
7. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the temperature of the division point of the low-nitrogen fraction and the high-nitrogen fraction is 320-360 ℃.
8. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the hydrofining reaction zone is provided with more than 3 hydrofining catalyst beds, and the hydrocracking reaction zone is provided with more than 1 hydrocracking catalyst bed.
9. A hydroprocessing process for treating a high nitrogen feed as recited in claim 8, wherein: the hydrofining reaction zone is provided with 3-5 hydrofining catalyst beds.
10. A hydroprocessing process for treating a high nitrogen feed as recited in claim 8, wherein: the hydrofining reaction zone is provided with 3-4 hydrofining catalyst beds.
11. The hydroprocessing process for treating high nitrogen feed stocks as recited in claim 8, wherein: the feed inlet at the middle lower part of the hydrofining reaction zone is positioned between any two hydrofining catalyst beds in the hydrofining reaction zone, and when 3 hydrofining catalyst beds are arranged, the feed inlet is arranged between the first hydrofining catalyst bed and the second hydrofining catalyst bed and/or between the second hydrofining catalyst bed and the third hydrofining catalyst bed.
12. A hydrogenation process for treating a high nitrogen feed as recited in claim 11, wherein: the feed inlet at the middle lower part of the hydrofining reaction zone is arranged between the two catalyst bed layers at the lowest part in the flowing direction of the liquid phase material.
13. A hydrogenation process for treating a high nitrogen feed as recited in claim 11, wherein: when 3 hydrofining catalyst beds are arranged, a feed inlet at the middle lower part of the hydrofining reaction zone is arranged between the second hydrofining catalyst bed and the third hydrofining catalyst bed.
14. A hydroprocessing process for treating a high nitrogen feed stock as recited in claim 1, wherein: hydrorefiningThe operating conditions of the reaction zone were: hydrogen partial pressure is 5-18 MPa, hydrogen-oil volume ratio is 500-5000, volume airspeed is 0.5-3 h -1 The reaction temperature is 260-420 ℃.
15. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the operating conditions of the hydrofining reaction zone are as follows: hydrogen partial pressure is 8-16 MPa, hydrogen-oil volume ratio is 700-1500, volume space velocity is 0.7-2 h -1 The reaction temperature is 300-400 ℃.
16. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the hydrocracking reaction zone has the operating conditions that the hydrogen partial pressure is 6-18 MPa, the hydrogen-oil volume ratio is 500-5000, and the volume space velocity is 0.2-5 h -1 The reaction temperature is 270-460 ℃.
17. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the hydrocracking reaction zone has the operating conditions that the hydrogen partial pressure is 7-17 MPa; the volume ratio of the hydrogen to the oil is 700-1500; the volume space velocity is 0.6 to 2 hours -1 (ii) a The reaction temperature is 300-400 ℃.
18. A hydroprocessing process for treating a high nitrogen feed stock as recited in claim 1, wherein: along the flowing direction of the liquid phase material, the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer above the feed inlet at the middle lower part is gradually reduced, and the difference of the pore volume of the hydrofining catalyst in the adjacent hydrofining catalyst bed layers is 0.03-0.22 mL/g.
19. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer below the middle-lower feed port is not less than that of the hydrofining catalyst in the hydrofining catalyst bed layer above the middle-lower feed port, and the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer at the top of the hydrofining reaction zone is 0.30-0.50 mL/g.
20. A hydroprocessing process for treating a high nitrogen feed stock as recited in claim 19, wherein: the pore volume of the hydrofining catalyst in the hydrofining catalyst bed layer at the uppermost part of the hydrofining reaction zone is 0.34-0.40 mL/g.
21. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: along the flowing direction of the liquid phase material, the content of active metal components of the hydrofining catalyst in the hydrofining catalyst bed layer above the feed inlet at the middle lower part is gradually reduced, and the content of the active metal components of the hydrofining catalyst in the hydrofining catalyst bed layers at two adjacent layers is 0.5-2.0 wt% different calculated by metal oxide; wherein, the content of the VIB group metal component is different from 0.5wt percent to 1.5wt percent; the difference of the VIII group metal component content is 0.2wt percent to 1.0wt percent.
22. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the content of active metal components of the hydrofining catalyst in the hydrofining catalyst bed layer below the feed inlet at the middle lower part is not less than the content of active metal components of the hydrofining catalyst in the hydrofining catalyst bed layer at the top of the hydrofining reaction zone, and the content of the active metal components is 0.1-5.0 wt% higher than that of the hydrofining catalyst in the hydrofining catalyst bed layer at the top in terms of metal oxides.
23. The hydroprocessing process for treating high nitrogen feed stocks as recited in claim 22, wherein: the content of active metal components in the hydrofining catalyst in the uppermost hydrofining catalyst bed is 0.5-2.0 wt% in terms of metal oxide.
24. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the hydrofining catalyst comprises an auxiliary agent fluorine, and along the flowing direction of liquid phase materials, the load capacity of fluorine in the hydrofining catalyst is sequentially increased, the load capacity of fluorine in the hydrofining catalyst in two adjacent hydrofining catalyst beds is sequentially increased by 0.2-2.0 wt%, and the load capacity of fluorine in the hydrofining catalyst is 0.1-7.0 wt%.
25. A hydrogenation process for treating a high nitrogen feed as recited in claim 1, wherein: the hydrofining catalyst comprises an auxiliary agent fluorine, and along the flow direction of liquid phase materials, the load capacity of fluorine in the hydrofining catalyst is increased in sequence, and the load capacity of fluorine in the hydrofining catalyst in two adjacent layers of hydrofining catalyst beds is increased by 0.3-0.5 wt% in sequence; the load capacity of fluorine in the hydrofining catalyst is 0.1-3.5 wt%.
26. A hydroprocessing system for treating a high nitrogen feedstock to implement a hydroprocessing process for treating a high nitrogen feedstock as recited in claim 1, said hydroprocessing system comprising:
a fractionating tower: receiving a high-nitrogen raw material, and separating to obtain a low-nitrogen fraction and a high-nitrogen fraction;
a hydrofining reaction zone: the hydrofining reaction zone comprises a top feeding hole, a middle lower feeding hole and a bottom discharging hole; the high-nitrogen fraction enters a hydrofining reaction zone through a top feed inlet, the low-nitrogen fraction enters a hydrofining reaction zone through a middle lower feed inlet, and the reaction is carried out in the presence of hydrogen and a hydrofining catalyst, so that a hydrofining reaction effluent is obtained after the reaction;
a hydrocracking reaction zone: leading out the hydrofining reaction effluent from a discharge port at the bottom of the hydrofining reaction zone, introducing the hydrofining reaction effluent into a hydrocracking reaction zone, and reacting in the presence of hydrogen and a hydrocracking catalyst;
the gas-liquid separation unit is used for receiving the reaction effluent from the hydrocracking reaction zone and separating the reaction effluent to obtain a gas-phase material and a liquid-phase material;
and the fractionating unit is used for receiving the liquid-phase material from the gas-liquid separation unit and separating the liquid-phase material to obtain gas, naphtha, aviation kerosene, diesel oil and tail oil.
27. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 26, wherein: the hydrofining reaction zone and the hydrocracking reaction zone are arranged in 1 reactor or respectively arranged in one or more independent reactors.
28. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 26, wherein: the hydrofining reaction zone is provided with more than 3 hydrofining catalyst beds, and the hydrocracking reaction zone is provided with more than 1 hydrocracking catalyst bed.
29. The hydroprocessing system for processing high nitrogen feed stock of claim 28, wherein: the hydrofining reaction zone is provided with 3-5 hydrofining catalyst beds.
30. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 28, wherein: the hydrofining reaction zone is provided with 3-4 hydrofining catalyst beds.
31. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 26, wherein: the aviation kerosene and/or diesel oil are circulated back to the hydrofining reaction zone through a pipeline.
32. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 31, wherein: the aviation kerosene and/or diesel oil enter the hydrofining reaction zone through the middle-lower part feed inlet to be mixed with the low-nitrogen fraction.
33. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 26, wherein: a feed inlet at the middle lower part of the hydrofining reaction zone is positioned between any two hydrofining catalyst beds in the hydrofining reaction zone, and when 3 hydrofining catalyst beds are arranged, the feed inlet is arranged between the first hydrofining catalyst bed and the second hydrofining catalyst bed and/or between the second hydrofining catalyst bed and the third hydrofining catalyst bed.
34. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 33, wherein: the feed inlet at the middle lower part of the hydrofining reaction zone is arranged between the two catalyst bed layers at the lowest part in the flowing direction of the liquid phase material.
35. The hydrogenation system for processing a high nitrogen feedstock as recited in claim 33, wherein: a feed inlet at the middle lower part of the hydrofining reaction zone is arranged between the second hydrofining catalyst bed layer and the third hydrofining catalyst bed layer.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618594A (en) * | 1979-03-19 | 1986-10-21 | Standard Oil Company (Indiana) | Catalyst and process for the hydrodenitrogenation and hydrocracking of high-nitrogen feeds |
| US6312586B1 (en) * | 1999-09-27 | 2001-11-06 | Uop Llc | Multireactor parallel flow hydrocracking process |
| CN1349554A (en) * | 1999-04-13 | 2002-05-15 | 切夫里昂美国公司 | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
| CN103805244A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of clean diesel oil with low condensation point |
| CN104611016A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Poor-quality raw material hydrocracking method |
| CN105838418A (en) * | 2016-06-13 | 2016-08-10 | 黑龙江省能源环境研究院 | Method for improving shale oil hydrorefining denitrification rate |
| CN111100698A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking method for high-dry-point high-nitrogen raw oil |
-
2020
- 2020-09-17 CN CN202010981455.1A patent/CN114196438B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618594A (en) * | 1979-03-19 | 1986-10-21 | Standard Oil Company (Indiana) | Catalyst and process for the hydrodenitrogenation and hydrocracking of high-nitrogen feeds |
| CN1349554A (en) * | 1999-04-13 | 2002-05-15 | 切夫里昂美国公司 | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
| US6312586B1 (en) * | 1999-09-27 | 2001-11-06 | Uop Llc | Multireactor parallel flow hydrocracking process |
| CN103805244A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Production method of clean diesel oil with low condensation point |
| CN104611016A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Poor-quality raw material hydrocracking method |
| CN105838418A (en) * | 2016-06-13 | 2016-08-10 | 黑龙江省能源环境研究院 | Method for improving shale oil hydrorefining denitrification rate |
| CN111100698A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrocracking method for high-dry-point high-nitrogen raw oil |
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